2,2′,2″-Nitrilotriacetonitrile

Nitrilotriacetonitril Strukturformel.svg 2,2′,2′′-Nitrilotriacetonitrile 7327-60-8 81762 86K27312YB C(C#N)N(CC#N)CC#N 73778 1S/C6H6N4/c7-1-4-10(5-2-8)6-3-9/h4-6H2 LJAIDEYQVIJERM-UHFFFAOYSA-N 4 6 6 CSD Entry: CIRWOR 2,2',2''-Nitrilotriacetonitrile Pnma orthorhombic 7.1085 9.9320 9.3869 06 07 08 301 302 312 315 319 335 373 260 261 264 270 271 280 301+310 301+312 302+352 304+340 305+351+338 312 314 321 322 330 332+313 337+313 362 363 403+233 405 501 Danger Nitrilotriacetonitrile (NTAN) is a precursor for nitrilotriacetic acid (NTA, a biodegradable complexing agent and building block for detergents), for tris(2-aminoethyl)amine (a tripodal tetradentate chelating agent known under the abbreviation tren) and for the epoxy resin crosslinker aminoethylpiperazine. Production The synthesis of nitrilotriacetonitrile is based on the basic building blocks ammonia, formaldehyde and hydrogen cyanide, which are reacted (via the triple cyanomethylation of the ammonia) in acidic aqueous medium in discontinuous or continuous processes. US 3337607 Process for preparation of an amine nitrile 1967-08-22 1965-01-25 J.C. Wollensak Ethyl Corp. US 3840581 Process for the manufacture of nitrilotriacetonitrile 1974-10-08 1970-05-26 H. Neumaier, W. Vogt, K. Sennewald, R. Schuller, G. Lenz Knapsack AG 200px|center|Synthesis of nitrilotriacetonitrile NTAN Ammonia is introduced as a gas, in form of hexamethylenetetramine US 3061628 Process and preparation of amino nitriles and acetic acids 1962-10-30 1958-09-12 J.J. Singer Jr., M. Weisberg Hampshire Chemical Corp. or as ammonium sulfate together with formaldehyde as aqueous solution (usually 37% by weight) at pH values <2 and treated with aqueous prussic acid solution or liquid hydrogen cyanide at temperatures around 100 °C. Prussic acid is used directly from the Andrussow process or the BMA process of Evonik Degussa EP 0102343 Process for producing nitrilotriacetonitrile 1986-02-26 1983-08-25 C.Y. Shen Monsanto Co. without pre-purification if necessary. When the mother liquors are returned, yields of more than 90% are achieved. Problematic, particularly in the case of a continuous process, is the tendency of NTAN to precipitate at temperatures below 90 °C which can lead to clogging of tube reactors and conduits and thermal runaway of the reaction.E. Fiedler Chem. Engineer. Transactions (CET) Emergency Runaway Reaction – What Precedes? What Follows? 48 361–366 978-88-95608-39-6 2016 10.3303/CET1648061 Properties Nitrilotriacetonitrile is a colorless and odorless solid which dissolves hardly in water but dissolves well in nitromethane and acetone.Product Stewardship Summary, Chelates: NTAN akzonobel.com Akzo Nobel Functional Chemicals https://www.akzonobel.com/dissolvine/system/images/AkzoNobel_NTAN_08-2011_tcm108-76620.pdf dead PDF; 45.7 KB 2017-03-20 https://web.archive.org/web/20130602043001/http://www.akzonobel.com/dissolvine/system/images/AkzoNobel_NTAN_08-2011_tcm108-76620.pdf 2013-06-02 Use Nitrilotriacetonitrile can be homopolymerized or copolymerized with iminodiacetonitrile in the melt in the presence of basic catalysts such as sodium methoxide to form dark-colored solid polymers which can be carbonized to form nitrogen-containing and electrically conductive polymers at temperatures above 1000 °C. US 3578643 New polymers from nitrilotriacetonitrile and iminodiacetonitrile 1971-05-11 1969-06-06 L.L. Wood, R.A. Hamilton W.R. Grace & Co. The products obtained have not found application as conductive polymers. The hydrogenation of NTAN first converts a cyano group into an imino group which attacks a cyano group (which are adjacent and sterically suitable for forming a six-membered ring) rather than being further hydrogenated to the primary amino group. The end product of the catalytic hydrogenation of nitrilotriacetonitrile is therefore 1-(2-aminoethyl)piperazine. 400px|center|Synthesis of aminoethylpiperazine by hydrogenation of NTAN If the catalytic hydrogenation of NTAN is carried out with e. g. Raney nickel in the presence of a large excess of ammonia, it gives tris(2-aminoethyl)amine. US 3565957 Hydrogenation of nitrilotriacetonitrile 1971-02-23 1968-09-20 S.B. Mirviss, D.J. Martin, E.D. Weil Stauffer Chemical Co.500px|center|Synthesis of tris (2-aminoethyl) amine(tren) Tris(2-aminoethyl)amine is used as a tetrazident complexing agent (abbreviated as "tren"), which forms stable chelates, particularly with divalent and trivalent transition metal ions.G. Anderegg V. Gramlich Helv. Chim. Acta 1:1 Metal Complexes of Bivalent Cobalt, Nickel, Copper, Zink, and Cadmium with the Tripodal Ligand tris[2-(dimethylamino)ethyl]amine: Their stabilities and the X-ray crystal structure of its copper(II) complex sulfate 77 3 685–690 1994 10.1002/hlca.19940770312 Nitrilotriacetonitrile reacts with methanal at pH 9.5 to give 2,2-dihydroxymethyl-nitrilotriacetonitrile, which is hydrolyzed with sodium hydroxide solution at 100 °C to give the trisodium salt of 2-hydroxymethylserine-N,N-diacetic acid, from which the free acid can be obtained by acidification in 51% yield. EP 0396999 2-Methyl- und 2-Hydroxymethyl-serin-N,N-diessigsäure und ihre Derivate 1990-11-14 1990-04-30 A. Oftring, S. Birnbach, R. Bauer, C. Gousetis, W. Trieselt BASF AG 450px|center|Synthesis of 2-hydroxymethylserine-N, N-diacetic acid trisodium salt from NTAN The compound is suitable as a complexing agent for heavy metal ions or alkaline earth metal ions, as a stabilizer for bleaching agents (e.g. for sodium perborate, in solid detergent preparations) and as a builder in detergents for inhibiting the formation of incrustations in textiles during laundering. The hydrolysis of nitrilotriacetonitrile with water in concentrated sulfuric acid yields under gentle conditions practically quantitatively nitrilotriacetamide, which has been investigated as a neutral tetradentate ligand for metal complexation.D.A. Smith S. Sucheck S. Cramer D. Baker Synth. Commun. Nitrilotriacetamide: Synthesis in concentrated sulfuric acid and stability in water 25 24 4123–4132 1995 10.1080/00397919508011491 At elevated temperature, 3,5-dioxopiperazine-1-acetamide is formed by ring closure, which can be quantitatively converted into the nitrilotriacetamide after neutralization and heating with excess aqueous ammonia. GB 1170399 A process for preparing 3,5-dioxo-1-piperazineacetamide and nitrilotriacetic acid triamide 1969-11-12 1968-06-12 W.R. Grace & Co.D.A. Smith S. Cramer S. Sucheck E. Skrzypzak-Jankun Tetrahedron Lett. Facile synthesis of substituted nitrilotriacetamides 33 50 7765–7768 1992 10.1016/0040-4039(93)88040-P 650px|center|Synthesis of nitrilotracetamide (and 3,5-dioxopiperazine-1-acetamide) Nitrilotriacetonitrile serves mainly as a raw material for the production of the biodegradable, but carcinogen suspected complexing agent nitrilotriacetic acid by acid or base-catalyzed US 4547589 Hydrolysis of nitrilotriacetonitrile 1985-10-15 1984-01-03 C.Y. Shen Monsanto Co. hydrolysis of the cyano groups. 500px|center|Alkaline hydrolysis of NTAN to NTA trisodium salt Undesirable residual contents of cyanide ions in the hydrolyzate can be removed by post-treatment with oxidizing agents such as sodium hypochlorite at pH 8.US 8362298 Hydrolyzed nitrilotriacetonitrile compositions, nitrilotriacetonitrile hydrolysis formulations and methods for making and using same O.M. Falana, A. Hikem, S.R. Kakadjian, F. Zamora 2013-01-29 2011-05-20 Clearwater International, LLC References Category:Amines Category:Nitriles